Process for the production of chlorinated propenes

ABSTRACT

Processes for the production of chlorinated propenes are provided. The present processes make use of a feedstock comprising 1,2,3-trichloropropane and chlorinates the 1,1,2,3-tetrachloropropane generated by the process prior to a dehydrochlorination step. Production of the less desirable pentachloropropane isomer, 1,1,2,3,3-pentachloropropane, is thus minimized. The present processes provide better reaction yield as compared to conventional processes that require dehydrochlorination of 1,1,2,3-tetrachloropropane prior to chlorinating the same. The present process can also generate anhydrous HCl as a byproduct that can be removed from the process and used as a feedstock for other processes, while limiting the production of waste water, thus providing further time and cost savings.

FIELD

The present invention relates to processes for the production ofchlorinated propenes.

BACKGROUND

Hydrofluorocarbon (HFC) products are widely utilized in manyapplications, including refrigeration, air conditioning, foam expansion,and as propellants for aerosol products including medical aerosoldevices. Although HFC's have proven to be more climate friendly than thechlorofluorocarbon and hydrochlorofluorocarbon products that theyreplaced, it has now been discovered that they exhibit an appreciableglobal warming potential (GWP).

The search for more acceptable alternatives to current fluorocarbonproducts has led to the emergence of hydrofluoro-olefin (HFO) products.Relative to their predecessors, HFOs are expected to exert less impacton the atmosphere in the form of a lesser, or no, detrimental impact onthe ozone layer and their much lower GWP as compared to HFC's.Advantageously, HFO's also exhibit low flammability and low toxicity.

As the environmental, and thus, economic importance of HFO's hasdeveloped, so has the demand for precursors utilized in theirproduction. Many desirable HFO compounds, e.g., such as2,3,3,3-tetrafluoroprop-1-ene or 1,3,3,3-tetrafluoroprop-1-ene, maytypically be produced utilizing feedstocks of chlorocarbons, and inparticular, chlorinated propenes, which may also find use as feedstocksfor the manufacture of polyurethane blowing agents, biocides andpolymers.

Unfortunately, many chlorinated propenes may have limited commercialavailability, and/or may only be available at prohibitively high cost,due at least in part to the complicated, multi-step processes typicallyutilized in their manufacture. For example, in methods that utilizeallyl chloride or 1,2,3-trichloropropane as starting materials,successive dehydrochlorinations and chlorinations with elementalchlorine may be done until the desired number of chlorine atoms has beenadded. Or, some conventional methods call for the chlorination ofchlorinated alkanes having fewer chlorine atoms than desired in thefinal product.

At some point in many, if not all, such processes, mixtures of isomersof tetrachloropropanes and pentachloropropanes may typically beproduced, that once produced, may either be difficult to remove and/orreact to produce undesirable by products. And so, many conventionalprocesses call for the removal of these isomers, thereby lowering theyield of such processes. And, doing so introduces additional cost andtime to an already multi-step and typically expensive process.Additionally, such processes may also result in the production of largeamounts of contaminated waste water having high quantities of sodiumchloride, and one or more chlorinated organic(s). The waste water thusmust typically be treated before releasing it to the environment,requiring even further expenditure. Any recovered sodium chlorideprovides little in the way of recoverable cost.

It would thus be desirable to provide improved processes for theproduction of chlorocarbon precursors useful as feedstocks in thesynthesis of refrigerants and other commercial products. Moreparticularly, such processes would provide an improvement over thecurrent state of the art if they were capable of minimizing, or eveneliminating, the production of the less desirable tetrachloropropanesand pentachloropropanes, and/or economically utilizing any amounts ofthe less desirable isomers that may be produced. Further benefit wouldbe realized if the processes would provide by-products of highercommercial or reuse value than sodium chloride.

BRIEF DESCRIPTION

The present invention provides efficient processes for the production ofchlorinated propenes. The processes make use of 1,2,3-trichloropropaneas a feedstock and reuse at least a portion of at least one lessdesirable tetra- or penta-chloropropane isomer. In so doing, theprocesses further minimize, or even eliminate the production of the lessdesirable hexachloropropane isomer, 1,1,2,2,3,3-hexachloropropane. As aresult, yield and/or selectivity of the process is enhanced overconventional chlorination processes that discard these isomers, and timeand cost savings are thus provided. Furthermore, the processes may makeuse of at least one catalytic dehydrochlorination step, in place of oneor more caustic dehydrochlorination step(s), and so waste waterproduction is minimized, as is the production of the low-valueby-product sodium chloride.

In one aspect, there is provided a process for the production ofchlorinated propenes from a feed stream comprising1,2,3-trichloropropane. The process comprises at least one chlorinationstep and at least one dehydrochlorination step. Advantageously, at leasta portion of the 1,2,2,3-tetrachloropropane produced by the process iseither recycled and/or further reacted, i.e., not discarded. The1,2,2,3-tetrachloropropane may either be recycled back to the feedstream, so that the feed stream comprises 1,2,3-trichloropropane and1,2,2,3-tetrachloropropane, or, in some embodiments, may be chlorinatedin a second chlorination step to provide 1,1,2,2,3-pentachloropropane.

In some embodiments, at least one dehydrochlorination step may beconducted in the presence of a catalyst, and in such embodiments,further improvements in process productivity are expected. Theseembodiments also provide for the minimization of the production of thelow value by-product sodium chloride, and instead, produce anhydrousHCl, which may be recovered from the process if desired. Usefulchlorinating agents may include chlorine, sulfuryl chloride, orcombinations of these.

The advantages provided by the present processes may be carried forwardby utilizing the chlorinated and/or fluorinated propenes or higheralkenes to produce further downstream products, such as, e.g.,2,3,3,3-tetrafluoroprop-1-ene or 1,3,3,3-tetrafluoroprop-1-ene.

DESCRIPTION OF THE FIGURES

The detailed description that follows may be further understood and/orillustrated when considered along with the attached figures.

FIG. 1 is a schematic diagram of a process according to one embodiment;and

FIG. 2 is a schematic diagram of a process according to a furtherembodiment.

DETAILED DESCRIPTION

The present specification provides certain definitions and methods tobetter define the present invention and to guide those of ordinary skillin the art in the practice of the present invention. Provision, or lackof the provision, of a definition for a particular term or phrase is notmeant to imply any particular importance, or lack thereof. Rather, andunless otherwise noted, terms are to be understood according toconventional usage by those of ordinary skill in the relevant art.

The terms “first”, “second”, and the like, as used herein do not denoteany order, quantity, or importance, but rather are used to distinguishone element from another. Also, the terms “a” and “an” do not denote alimitation of quantity, but rather denote the presence of at least oneof the referenced item, and the terms “front”, “back”, “bottom”, and/or“top”, unless otherwise noted, are merely used for convenience ofdescription, and are not limited to any one position or spatialorientation.

If ranges are disclosed, the endpoints of all ranges directed to thesame component or property are inclusive and independently combinable(e.g., ranges of “up to 25 wt. %, or, more specifically, 5 wt. % to 20wt. %,” is inclusive of the endpoints and all intermediate values of theranges of “5 wt. % to 25 wt. %,” etc.). As used herein, percent (%)conversion is meant to indicate change in molar or mass flow of reactantin a reactor in ratio to the incoming flow, while percent (%)selectivity means the change in molar flow rate of product in a reactorin ratio to the change of molar flow rate of a reactant.

Reference throughout the specification to “one embodiment” or “anembodiment” means that a particular feature, structure, orcharacteristic described in connection with an embodiment is included inat least one embodiment. Thus, the appearance of the phrases “in oneembodiment” or “in an embodiment” in various places throughout thespecification is not necessarily referring to the same embodiment.Further, the particular features, structures or characteristics may becombined in any suitable manner in one or more embodiments.

In some instances, “TCP” may be used herein as an abbreviation for1,2,3-trichloropropane, “ACL” may be used as an abbreviation for allylchloride or 3-chloropropene, and “TCPE” may be used as an abbreviationfor 1,1,2,3-tetrachloropropene. The terms “cracking” and“dehydrochlorination” are used interchangeably to refer to the same typeof reaction, i.e., one resulting in the creation of a double bondtypically via the removal of hydrogen and a chlorine atom from adjacentcarbon atoms in chlorinated hydrocarbon reagents.

The present invention provides efficient processes for the production ofchlorinated propenes. The present processes comprise conducting at leastone chlorination step and at least one dehydrochlorination step on afeedstream comprising TCP, either alone, or in some embodiments, incombination with one or more other chlorinated alkanes or alkenes, e.g.,allyl chloride. At least a portion of the 1,2,2,3-tetrachloropropanegenerated by the process is reused within the process, i.e., is eitherrecycled to the feedstream, or further reacted. Conventional processeshave typically called for the removal of 1,2,2,3-tetrachloropropane fromsuch processes as generated, presumably operating under the assumptionthat the presence of this isomer would result in the production offurther undesirable by-products and/or isomers. The present inventorshave now recognized that this is not the case, and that instead, use canbe made of the generated 1,2,2,3-tetrachloropropane, thereby increasingthe yield and efficiency of the process. Thus, the present process ismore economically attractive than conventional processes that requirethat this isomer be removed.

Catalysts are not required for the chlorination steps of the presentprocess, but can be used, if desired, in order to increase the reactionkinetics. For example, free radical catalysts or initiators may be usedto enhance the present process. Such catalysts may typically compriseone or more chlorine, peroxide or azo-(R—N═N—R′) groups and/or exhibitreactor phase mobility/activity. As used herein, the phrase “reactorphase mobility/activity” means that a substantial amount of the catalystor initiator is available for generating free radicals of sufficientenergy which can initiate and propagate effective turnover of theproduct, the chlorinated and/or fluorinated propene(s), within thedesign limitations of the reactor.

Furthermore, the catalyst/initiator should have sufficient homolyticdissociation energies such that the theoretical maximum of free radicalsis generated from a given initiator under the temperature/residence timeof the process. It is especially useful to use free radical initiatorsat concentrations where free radical chlorination of incipient radicalsis prevented due to low concentration or reactivity. Surprisingly, theutilization of the same, does not result in an increase in theproduction of impurities by the process, but does provide selectivitiesto the chlorinated propenes of at least 50%, or up to 60%, up to 70%,and in some embodiments, up to 80% or even higher.

Such free radical initiators are well known to those skilled in the artand have been reviewed, e.g., in “Aspects of some initiation andpropagation processes,” Bamford, Clement H. Univ. Liverpool, Liverpool,UK., Pure and Applied Chemistry, (1967), 15 (3-4), 333-48 and Sheppard,C. S.; Mageli, O. L. “Peroxides and peroxy compounds, organic,”Kirk-Othmer Encycl. Chem. Technol., 3rd Ed. (1982), 17, 27-90.

Taking the above into consideration, examples of suitablecatalysts/initiators comprising chlorine include, but are not limited tocarbon tetrachloride, hexachloroacetone, chloroform, hexachloroethane,phosgene, thionyl chloride, sulfuryl chloride, trichloromethylbenzene,perchlorinated alkylaryl functional groups, or organic and inorganichypochlorites, including hypochlorous acid, and t-butylhypochlorite,methylhypochlorite, chlorinated amines (chloramine) and chlorinatedamides or sulfonamides such as chloroamine-T®, and the like. Examples ofsuitable catalysts/initiators comprising one or more peroxide groupsinclude hydrogen peroxide, hypochlorous acid, aliphatic and aromaticperoxides or hydroperoxides, including di-t-butyl peroxide, benzoylperoxide, cumyl peroxide and the like. Diperoxides offer an advantage ofnot being able to propagate competitive processes (e.g., the freeradical chlorination of PDC to TCP (and its isomers) andtetrachloropropanes). In addition, compounds comprising azo-groups, suchas azobisisobutyronitrile (AIBN), 1,1′-azobis(cyclohexanecarbonitrile(ABCN), 2,2′-azobis(2,4-dimethyl valeronitrile), and dimethyl2,2′-azobis(2-methylpropionate), may have utility in effecting thechlorination of PDC to trichloropropanes and tetrachloropropanes underthe conditions of this invention. Combinations of any of these may alsobe utilized.

The process or reactor zone may be subjected to pulse laser orcontinuous UV/visible light sources at a wavelength suitable forinducing photolysis of the free radical catalyst/initiator, as taught byBreslow, R. in Organic Reaction Mechanisms W.A. Benjamin Pub, New York p223-224. Wavelengths from 300 to 700 nm of the light source aresufficient to dissociate commercially available radical initiators. Suchlight sources include, e.g., Hanovia UV discharge lamps, sunlamps oreven pulsed laser beams of appropriate wavelength or energy which areconfigured to irradiate the reactor chamber. Alternatively, chloropropylradicals may be generated from microwave discharge into abromochloromethane feedsource introduced to the reactor as taught byBailleux et al., in Journal of Molecular Spectroscopy, 2005, vol. 229,pp. 140-144.

In some embodiments, ionic chlorination catalysts may be utilized in oneor more chlorination steps. The use of ionic chlorination catalysts inthe present process is particularly advantageous since theydehydrochlorinate and chlorinate alkanes at the same time. That is,ionic chlorination catalysts remove a chlorine and hydrogen fromadjacent carbon atoms, the adjacent carbon atoms form a double bond, andHCl is released. A chlorine molecule is then added back, replacing thedouble bond, to provide a higher chlorinated alkane.

Ionic chlorination catalysts are well known to those or ordinary art andany of these may be used in the present process. Exemplary ionicchlorination catalysts include, but are not limited to, aluminumchloride, ferric chloride (FeCl₃) and other iron containing compounds,iodine, sulfur, antimony pentachloride (SbCl₅), boron trichloride(BCl₃), lanthanum halides, metal triflates, and combinations thereof. Ifcatalysts are to be utilized in one or more of the chlorination steps ofthe present process, the use of ionic chlorination catalysts, such asAlCl₃ and I₂, can be preferred.

The dehydrochlorination steps of the present process may similarly beconducted without a catalyst, in the presence of a liquid caustic.Although vapor phase dehydrochlorinations advantageously result in theformation of a higher value byproduct than liquid phasedehydrochlorinations, liquid phase dehydrochlorination reactions canprovide cost savings since evaporation of reactants is not required. Thelower reaction temperatures used in liquid phase reactions may alsoresult in lower fouling rates than the higher temperatures used inconnection with gas phase reactions, and so reactor lifetimes may alsobe optimized when at least one liquid phase dehydrochlorination isutilized.

Many chemical bases are known in the art to be useful for liquid causticcracking, and any of these can be used. For example, suitable crackingbases include, but are not limited to, alkali metal hydroxides, such assodium hydroxide, potassium hydroxide, calcium hydroxide; alkali metalcarbonates such as sodium carbonate; lithium, rubidium, and cesium orcombinations of these. Phase transfer catalysts such as quaternaryammonium and quaternary phosphonium salts (e.g. benzyltrimethylammoniumchloride or hexadecyltributylphosphonium bromide) can also be added toimprove the dehydrochlorination reaction rate with these chemical bases.

In some alternative embodiments, one or more of the dehydrochlorinationsteps of the present process may be carried out in the presence of acatalyst so that the use of liquid caustic is reduced, or eveneliminated, from the process. In such embodiments, suitabledehydrochlorination catalysts include, but are not limited to, ferricchloride (FeCl₃). Other suitable examples of vapor phasedehydrochlorination catalysts known to those of ordinary skill in theart are disclosed in International Patent Application No. WO 2009/015304A1.

Any or all of the chlorination and/or dehydrochlorination catalysts canbe provided either in bulk or in connection with a substrate, such asactivated carbon, graphite, silica, alumina, zeolites, fluorinatedgraphite and fluorinated alumina. Whatever the desired catalyst (ifany), or format thereof, those of ordinary skill in the art are wellaware of methods of determining the appropriate concentration and methodof introduction thereof. For example, many catalysts are typicallyintroduced into the reactor zone as a separate feed, or in solution withother reactants, e.g., TCP.

The amount of any chlorination catalyst and/or dehydrochlorinationcatalyst utilized will depend upon the particular catalyst chosen aswell as the other reaction conditions. Generally speaking, in thoseembodiments of the invention wherein the utilization of a catalyst isdesired, enough of the catalyst should be utilized to provide someimprovement to reaction process conditions (e.g., a reduction inrequired temperature) or realized products, but yet not be more thanwill provide any additional benefit, if only for reasons of economicpracticality.

For purposes of illustration only then, it is expected, that usefulconcentrations of an ionic chlorination catalyst or free radicalinitiator will range from 0.001% to 20% by weight, or from 0.01% to 10%,or from 0.1% to 5 wt. %, inclusive of all subranges therebetween. If adehydrochlorination catalyst is utilized for one or moredehydrochlorination steps, useful concentrations may range from 0.01 wt.% to 5 wt. %, or from 0.05 wt. % to 2 wt. % at temperatures of from 70°C. to 200° C. If a chemical base is utilized for one or moredehydrochlorinations, useful concentrations of these will range from0.01 to 20 grmole/L, or from 0.1 grmole/L to 15 grmole/L, or from 1grmole/L to 10 grmole/L, inclusive of all subranges therebetween.Concentrations of each catalyst/base are given relative to the feed,e.g., 1,2,3-trichloropropane.

The present process can make use of a feedstock comprising1,2,3-trichloropropane to produce the desired chlorinated propenes. Theprocess feedstock may also comprise recycled alkanes, including recycled1,2,2,3-tetrachloropropane, or other chlorinated alkanes, if desired.And, the 1,2,3-trichloropropane may be generated within, or upstream of,the process, if desired, by any methods known to those of ordinary skillin the art.

The chlorination steps of the process may be carried out using anychlorination agent, and several of these are known in the art. Forexample, suitable chlorination agents include, but are not limited tochlorine, and/or sulfuryl chloride (SO₂Cl₂). Combinations ofchlorinating agents may also be used. Either or both Cl₂ and sulfurylchloride may be particularly effective when aided by the use of theaforementioned ionic chlorination catalysts.

Any chlorinated propene may be produced using the present method,although those with 3-5 chlorine atoms are particularly commerciallyattractive, and production of the same may thus be preferred in someembodiments. In some embodiments, the process may be used in theproduction of 1,1,2,3-tetrachloropropene, which may be a preferredfeedstock for refrigerants, polymers, biocides, etc.

In additional embodiments, one or more reaction conditions of theprocess may be optimized, in order to provide even further advantages,i.e., improvements in selectivity, conversion or production of reactionby-products. In certain embodiments, multiple reaction conditions areoptimized and even further improvements in selectivity, conversion andproduction of reaction by-products produced can be seen.

Reaction conditions of the process that may be optimized include anyreaction condition conveniently adjusted, e.g., that may be adjusted viautilization of equipment and/or materials already present in themanufacturing footprint, or that may be obtained at low resource cost.Examples of such conditions may include, but are not limited to,adjustments to temperature, pressure, flow rates, molar ratios ofreactants, etc.

That being said, the particular conditions employed at each stepdescribed herein are not critical, and are readily determined by thoseof ordinary skill in the art. What is important is that at least aportion of any 1,2,2,3-tetrachloropropane generated by the process isutilized by the process, i.e., either recycled as is, further reacted,or further reacted and recycled. It is also advantageous that at leastone dehydrochlorination step be conducted catalytically, rather than byusing liquid caustic, so that anhydrous HCl is produced and theproduction of sodium chloride is minimized. Those of ordinary skill inthe art will readily be able to determine suitable equipment for eachstep, as well as the particular conditions at which the chlorination,dehydrochlorination, separation, drying and isomerization steps may beconducted.

In the present process, 1,2,3-trichloropropane is converted to TCPEusing at least one chlorination step and at least onedehydrochlorination step. Importantly and advantageously, at least aportion of any 1,2,2,3-tetrachloropropane generated by the process isutilized within the process. That is, at least a portion of any1,2,2,3-tetrachloropropane may be recycled to the feedstock, or furtherreacted to provide intermediates more useful in the production of TCPE.

More specifically, and in one exemplary embodiment, a feed streamcomprising TCP is fed to a liquid phase chlorination reactor, e.g., suchas a batch or continuous stirred tank reactor with an internal coolingcoil. A shell and multitube reactor followed by vapor liquiddisengagement tank or vessel can also be used. Suitable reactionconditions include, e.g., temperatures of from ambient temperature(e.g., 20° C.) to 200° C., or from 30° C. to 150° C., or from 40° C. to120° C. or from 50° C. to 100° C. Ambient pressure may be used, orpressures of from 100 kPa to 1000 kPa, or from 100 kPa to 500 kPa, orfrom 100 kPa to 300 kPa. At such conditions, the TCP is chlorinated totetra- and penta-chlorinated propanes at per pass conversions of greaterthan 10%, or 30%, or 50%, or 60%, or even up to 80% can be seen. The perpass conversion and reaction conditions are chosen or optimized suchthat the products of the first chlorination step consist of a mixture oftetrachloropropane and pentachloropropane while minimizing the formationof hexachloropropane to less than 10%.

The chlorination(s) may be conducted neat, i.e., in the absence ofsolvent, or, one or more solvents may be provided to the chlorinationreactor, and may be provided as a component of the feedstock, or,recycled from one or more separation columns operatively disposed toreceive streams from the chlorination reactor. For example,chloropropane intermediates may be recycled back to the chlorinationreactor from one separation column, and tri- and tetrachloropropaneintermediates may be recycled from another separation column. Inaddition, or as an alternative, the chlorination reactor may be providedwith a feed of any solvent appropriate for chlorination reactions, suchas, e.g., carbon tetrachloride, sulfuryl chloride,1,1,2,3,3-pentachloropropane, 1,1,2,2,3,3-hexachloropropane, otherhexachloropropane isomers, or a combination of these. In someembodiments, at least a portion of the 1,2,2,3-tetrachloropropane thatis generated by, and reused within, the process is recycled to the firstchlorination reactor.

The overhead vapor from the chlorination reactor, is cooled, condensedand fed to a first separation column, e.g., a distillation column thatmay be used to recover anhydrous HCl from an overhead stream thereof.This separation column is operated at conditions effective to provideanhydrous HCl to an overhead line thereof and chlorine through a bottomrecycle line.

More particularly, the top temperature of separation column for therecovery of HCl may typically be set below 0° C. or more preferably, canbe set at a temperature of from −70° C. to −10° C. The bottomtemperature of such a column is desirably set at from 10° C. to 150° C.,or from 30° C. to 100° C., with the exact temperature dependent to somedegree on the bottom mixture composition. The pressure of thisseparation column is desirably set above 200 kPa or preferably, from 500kPA to 2000 kPa, or more preferably from 500 kPa to 1000 kPa. The bottomstream of a column operated at such conditions would be expected tocontain excess chlorine, unreacted TCP, while the overhead stream wouldbe expected to comprise anhydrous HCl.

The bottoms liquid product stream from the first chlorination reactormay be fed to a second separation column operated at conditionseffective to separate the unreacted TCP and tetrachloropropane isomersfrom the 1,1,2,3-tetrachloropropane, pentachloropropanes, and heavierbyproducts. Such a separation may be achieved, e.g., by feeding thebottoms liquid stream to a separation column operating with a reboilertemperature lower than 180° C. and at a pressure at or less thanatmospheric.

The tetrachloropropane isomers are then desirably separated into atleast two streams—one stream comprising 1,2,2,3-tetrachloropropane(having a boiling point of 163° C.) and unreacted TCP (having a boilingpoint of 157° C.) and the other comprising 1,1,2,3-tetrachloropropane(having a boiling point of 179° C.). The 1,1,2,3-tetrachloropropane maythen be dehydrochlorinated as described in the art, e.g., by U.S. Pat.No. 3,823,195.

Advantageously, the stream of TCP and 1,2,2,3-tetrachloropropane maythen be recycled to the first chlorination reactor, or, separated toprovide streams comprising TCP and 1,2,2,3-tetrachloropropane, e.g., viaa separation column operating with a bottoms temperature of lower than165° C. and at a pressure at or less than atmospheric. In the latterembodiment, the separated TCP is then recycled to the first chlorinationreactor and the 1,2,2,3-tetrachloropropane further chlorinated toprovide 1,1,2,2,3-pentachloropropane, or dehydrochlorinated andchlorinated to provide 1,1,2,2,3-pentachloropropane. Either embodimentis advantageous over conventional methods that call for the removal anddisposal of this isomer.

If the thus separated 1,2,2,3-tetrachloropropane is desirably furtherchlorinated, rather than, or in addition to, a portion it beingrecycled, such a chlorination may desirably be carried out in a liquidphase chlorination reactor separate from, and operated at differentconditions than, the first chlorination reactor. More specifically,1,2,2,3-tetrachloropropane may be chlorinated to provide1,1,2,2,3-pentachloropropane by feeding the same to a continuous stirredtank reactor operated at conditions sufficient to provide from 10% to80%, or preferably from 10% to 40% per pass conversion of1,2,2,3-tetrachloropropane at the reactor effluent, e.g., at atemperature of from 30° C. to 120° C. and at pressures of ambientpressure or higher. When so operated, this chlorination reaction wouldbe expect to provide conversions of 1,2,2,3-tetrachloropropane of lessthan 80% with selectivity to 1,1,2,2,3-pentachloropane of from 0% to95%.

The output from the second chlorination reactor may then be fed to aseparation column operated at conditions effective to separate thesecond chlorination reaction stream into an overhead stream comprisingchlorine and HCl and a bottoms stream comprising unreacted1,2,2,3-tetrachloropropane, the desired pentachloropropane isomers andheavier by-products. The overhead stream may be further separated andpurified to provide a stream of chlorine, which may be recycled to thefirst chlorination reactor, if desired, and a stream of HCl, which maybe provided to the first separation column for the recovery of anhydrousHCl, as described above.

The bottoms stream from the second chlorination reactor may be fed tothe second separation column that also receives feed from the firstchlorination reactor. The bottom stream of this column comprisesproducts with boiling points higher than 1,2,2,3-tetrachloropropane,e.g. 1,1,2,3-tetrachloropropane, pentachloropropanes, and heavierbyproducts. This bottom stream is then fed to a third separation columnoperated such that the overhead stream comprises1,1,2,3-tetrachloropropane and the bottom stream comprisespentachloropropanes isomers and heavier byproducts. As well known in theart, this overhead stream can then be dehydrochlorinated using causticto produce trichloropropene isomers, e.g., as described in U.S. Pat. No.3,823,195.

The trichloropropenes from the bottoms stream can then be furtherchlorinated to pentachloropropane isomers in a separate chlorinationreactor operated at a temperature of from 50° C. to 80° C. The resultingpentachloropropanes are then combined with the bottom stream of a thirdseparation column comprising other pentachloropropane intermediates.

As an alternative to chlorinating the 1,2,2,3-tetrachloropropane to1,1,2,2,3-pentachloropropane, this tetrachloropropane isomer can bedehydrochlorinated at high yield to 1,2,3-trichloropropene. Thistrichloropropane intermediate is then readily chlorinated in liquidphase to 1,1,2,2,3-pentachloropropane as known in the art. In this case,the 1,2,2,3-tetrachloropropane can be optionally be combined with1,1,2,3-tetrachloropropane before the caustic dehydrochlorination stepdescribe above.

The bottom stream of the third separation column comprisingpentachloropropanes isomers is then further fed to a fourth separationcolumn operated at conditions effective to provide a bottom streamcomprising the less desirable pentachloropropane isomer,1,1,2,3,3-pentachloropropane, and heavier chlorinated reaction products,which is purged, and an overhead stream comprising the desirablepentachloropropane isomers, 1,1,1,2,3-pentachloropropane and1,1,2,2,3-pentachloropropane. In some embodiments, this overhead streamcan then be catalytically dehydrochlorinated, e.g., using iron or aniron containing catalyst, such as FeCl₃ so that the high valueby-product anhydrous HCl is produced. In other embodiments, the overheadstream can be dehydrochlorinated to the desired tetrachloropropaneproduct(s) using caustic or other chemical bases, as described above.

More specifically, a catalytic dehydrochlorination reactor may typicallybe a batch or a continuous stirred tank reactor. The mixing can be done,e.g., by mechanical or jet mixing of feed streams. Those of ordinaryskill in the art are readily able to determine the appropriateconditions at which to run a dehydrochlorination reactor in order toconduct the aforementioned dehydrochlorination. The catalyticdehydrochlorination of 1,1,1,2,3-pentachloropropane provides2,3,3,3-tetrachloropropene and 1,1,2,3-tetrachloropropene, as well asHCl that may advantageously be recovered by recycling the waste streamfrom the reactor to the initial anhydrous HCl recovery column.

The reaction stream from the catalytic dehydrochlorination reactor isthen fed to a further separation column to separate the desiredchlorinated propene, e.g., 1,1,2,3-TCPE, from the remaining stream,which is expected to comprise mostly 1,1,2,2,3-pentachloropropane. Thisstream of 1,1,2,2,3-pentachloropropane is then caustic cracked toprovide a mixture of 1,1,2,3-TCPE and 2,3,3,3-TCPE. The reaction streamfrom the caustic dehydrochlorination reactor may optionally be fed to adrying column, and the dried stream therefrom provided to a furtherreactor to isomerize the 2,3,3,3-tetrachloropropene to1,1,2,3-tetrachloropropene under the appropriate conditions.

For example, catalysts may be utilized to assist in the isomerization,in which case, suitable catalysts include, but are not limited to (i)siliceous granules having a polar surface including kaolinite,bentonite, and attapulgite; (ii) other mineral salts of silica such assaponite, quartz, (iii) siliceous non-mineral substance such as silicagel, fumed silica, and glass, or combinations of any of these. Suitableconditions for drying columns for such reaction streams are also knownto those of ordinary skill in the art, as evidenced by U.S. Pat. No.3,926,758

A schematic illustration of such a process is shown in FIG. 1. As shownin FIG. 1, process 100 would make use of chlorination reactors 102 and110, separation columns 104, 106, 108, 112, and 113, dehydrochlorinationreactors 114, 118 and 119, dryers 120 and 121 and isomerization reactor122. In operation, 1,2,3-trichloropropane (alone or, in someembodiments, in combination with recycled 1,2,2,3-tetrachloropropaneand/or allyl chloride) and the desired chlorination agent (e.g.,chlorine, SO₂Cl₂, or combinations of these) are fed to chlorinationreactor 102, which may be operated at any set of conditions operable toprovide for the chlorination of allyl chloride to TCP and/or thechlorination of TCP to tetra- and pentachlorinated propanes and known tothose of ordinary skill in the art.

The overhead stream of chlorination reactor 102 is provided toseparation column 104, which may desirably be a distillation column. Thefeed to the HCl separation column is preferably totally condensed liquidat temperature −40° C. to 0° C. made by applying a fractionation methodsuch as that described in U.S. Pat. No. 4,010,017. Separation column 104is operated at conditions effective to provide anhydrous HCl through anoverhead line thereof and chlorine and unreacted TCP to chlorinationreactor 102.

The bottom stream of reactor 102 is provided to separation column 106,which is operated at conditions effective to provide an overhead streamcomprising TCP and 1,2,2,3-tetrachloropropane and a bottoms streamcomprising other tetrachloropropane isomers, pentachloropropanes andheavier reaction by-products. The overhead stream from separation column106 may be recycled to first chlorination reactor 102, while the bottomsstream from separation column 106 is fed to further separation column108.

Separation column 108 separates the bottom stream from separation column106 into an overhead stream comprising 1,1,2,3-tetrachloropropane andthe desirable pentachloropropane isomers (1,1,2,2,3-pentachloropropaneand 1,1,1,2,3-pentachloropropane) and a bottom stream comprising theless desirable 1,1,2,3,3-pentachloropropane, hexachloropropane andheavier by-products. The overhead stream is fed to separation column112, while the bottoms stream is appropriately disposed of Separationcolumn 112 separates the overhead stream from separation column 108 intoan overhead stream comprising 1,1,2,3-tetrachloropropane and a bottomsstream comprising desired pentachloropropanes isomers, e.g., 1,1,2,2,3and 1,1,1,2,3-pentachloropropane. The 1,1,2,3-tetrachloropropane is thencaustic cracked in dehydrochlorination reactor 114 to providetrichloropropene intermediates.

The reaction liquid from dehydrochlorination reactor 114 is fed to dryercolumn 120 and the dried stream fed to chlorination reactor 110. Excesschlorine from chlorination reactor 110 may be recycled to separationcolumn 104, if desired. The product stream from chlorination reactor110, expected to comprise 1,1,2,2,3 and 1,1,1,2,3-pentachloropropane, isfed to dehydrochlorination reactor 118, where it is combined with thebottoms from stream separation column 112 that also comprises 1,1,2,2,3-and 1,1,1,2,3-pentachloropropane.

Within dehydrochlorination reactor 118, the desirable pentachloropropaneisomers are catalytically dehydrochlorinated to provide2,3,3,3-tetrachloropropene and 1,1,2,3-tetrachloropropene. Morespecifically, dehydrochlorination reactor may be charged with, e.g.,iron or an iron containing catalyst such as FeCl₃ and operated atpressures of from ambient to 400 kPA, at temperatures of from 40° C. to150° C. and with residence times of less than 3 hours.

The bottom reaction stream from dehydrochlorination reactor 118 is fedto separation column 113, while the overhead stream, comprisinganhydrous HCl, is provided to separation column 104 for purification andrecovery of anhydrous HCl. The bottom stream from dehydrochlorinationreactor 118, comprising tetrachloropropene products and unreactedpentachloropropanes, is then fed to separation column 113.

Separation column 113 is operated at conditions effective to separatethe desired chlorinated propene, e.g., 1,1,2,3-TCPE, as an overheadstream from the remaining by-products, e.g.,1,1,2,2,3-pentachloropropane. The bottoms stream from separation column113 is fed to caustic dehydrochlorination reactor 119, and the productstream thereof provided to drying column 121. The dried stream fromdrying column 121 is provided to isomerization reactor 122 to isomerizethe 2,3,3,3-tetrachloropropene to 1,1,2,3-tetrachloropropene under theappropriate conditions.

An additional embodiment of the process is shown in FIG. 2. This processis very similar to that shown in FIG. 1, with the exception of theinclusion of additional separation column 205 and third chlorinationreactor 203. In operation, rather than recycling the overhead streamfrom separation column 206 to chlorination reactor 202, the overheadstream from separation column 206 is fed to separation column 205.Separation column 205 is operated such that the overhead stream,expected to comprise unreacted TCP and 1,2,2,3-tetrachloropropane, isseparated to an overhead stream comprising TCP, recycled back to firstchlorination reactor 202, and a bottoms stream comprising1,2,2,3-tetrachloropropane. The bottoms stream is fed to third, liquidphase chlorination reactor 203, wherein it is used to produce anoverhead stream comprising HCl and a bottoms stream comprising unreacted1,2,2,3-tetrachloropropane and 1,1,2,2,3-pentachloropropane. Theoverhead stream from chlorination reactor 203 is fed to separationcolumn 204 that provides anhydrous HCl through an overhead line, whilethe bottoms stream is fed back to separation column 206 to recover theunreacted tetrachloropropane reactant.

In this example, third chlorination reactor 203 is desirably operated atdifferent conditions than the first chlorination reactor 202, i.e.,chlorination reactor 203 is desirably operated at conditions such thatthe production of hexachloropropane is minimized in the bottom stream.As a result, the overall yield of the process is improved.

The chlorinated propenes produced by the present process may typicallybe processed to provide further downstream products includinghydrofluoroolefins, such as, for example, 1,3,3,3-tetrafluoroprop-1-ene(HFO-1234ze). Since the present invention provides an improved processfor the production of chlorinated propenes, it is contemplated that theimprovements provided will carry forward to provide improvements tothese downstream processes and/or products. Improved methods for theproduction of hydrofluoroolefins, e.g., such as2,3,3,3-tetrafluoroprop-1-ene (HFO-1234yf), are thus also providedherein.

The conversion of chlorinated propenes to provide hydrofluoroolefins maybroadly comprise a single reaction or two or more reactions involvingfluorination of a compound of the formula C(X)_(m)CCl(Y)_(n)(C)(X)_(m)to at least one compound of the formula CF₃CF═CHZ, where each X, Y and Zis independently H, F, Cl, I or Br, and each m is independently 1, 2 or3 and n is 0 or 1. A more specific example might involve a multi-stepprocess wherein a feedstock of a chlorinated propene is fluorinated in acatalyzed, gas phase reaction to form a compound such as1-chloro-3,3,3-trifluoropropene (1233zd). The1-chloro-2,3,3,3-tetrafluoropropane is then dehydrochlorinated to2,3,3,3-tetrafluoroprop-1-ene or 1,3,3,3-tetrafluoroprop-1-ene via acatalyzed, gas phase reaction.

Example 1

50 mL 123-trichloropropane and 500 mg dimethyl2,2′-azobis(2-methylpropionate) are added to a tubular reactor at apressure of 150 psig. The reactor is sealed and Cl₂ flow started (30%v/v, 200 sccm). The reactor is then heated to 70° C. After 200 min at70° C., 23% conversion of the TCP is observed, with the product streamcomprising 1,1,2,3-tetrachloropropane, 1,2,2,3-tetrachloropropane,1,1,2,2,3-pentachloropropane, and 1,1,2,3,3-pentachloropropane (11233),with selectivities of 59.7%, 37.2%, 2.0%, and 1.2% respectively. The1,1,2,3-tetrachloropropane is then separated from the product mixtureand the reactor purged.

Carbon tetrachloride (45 mL) is added to the reactor and the reactorsealed and pressurized to 150 psi using Cl₂ (30% in N₂). Additional Cl₂is added for ˜20 minutes and then the reactor is heated to 70° C. Thereactor was sealed (reactor pressure ˜150 psig) and a mixture of the1,2,2,3-tetrachloropropane (1223) (3 mL) provided as described above,CCl₄ (7 mL) and dimethyl 2,2′-azobis(2-methylpropionate) (20 mg) isadded (t=0). The mixture is stirred at 70° C. for ˜90 minutes andsamples are periodically taken. Table 1, below, shows the productdistribution, expressed as molar % of the total product stream, as afunction of time. As shown by Table 1, recycling of the1,2,2,3-tetrachloropropane produced in a first chlorination reaction, toa further chlorination reaction wherein the 1,2,2,3 conversion is lessthan, e.g., 20%, results in the production of the desired intermediate1,1,2,2,3-pentachloropropane (11223) with less than 3.3% molarselectivity to the undesired 1,1,2,2,3,3-hexachloropropane (112233).

TABLE 1 Time (min) 5 21 60 1,2,2,3-tetrachloropropane 94.28 89.77 82.681,1,2,2,3-pentachloropropane 5.64 10.01 16.751,1,2,2,3,3-hexachloropropane 0.08 0.22 0.57 Selectivity to 1,1,2,2,3-98.6 97.9 96.7 pentachloropropane (%)

1. A process for the production of chlorinated propenes from afeedstream comprising 1,2,3-trichloropropane, comprising at least onechlorination step and at least one dehydrochlorination step, wherein1,2,2,3-tetrachloropropane produced by the process is recycled and/orfurther reacted.
 2. The process of claim 1, wherein the chlorinationstep produces a mixture comprising tetrachloropropanes andpentachloropropanes.
 3. The process of claim 2, wherein the mixture isseparated to provide a stream comprising the 1,2,2,3-tetrachloropropane.4. The process of claim 3, wherein the 1,2,2,3-tetrachloropropane streamis recycled to the first chlorination step.
 5. The process of claim 3,wherein the 1,2,2,3-tetrachloropropane stream is chlorinated in a secondchlorination step to provide 1,1,2,2,3-pentachloropropane.
 6. Theprocess of claim 3, wherein the separation further provides a stream ofunreacted 1,2,3-trichloropropane that is recycled to a chlorinationstep.
 7. The process of claim 3, wherein the separation further providesa stream of HCl and a stream comprising unreacted Cl₂, wherein the HClis recovered from the process as anhydrous HCl and the Cl₂ is recycled.8. The process of claim 3, wherein the separation further provides astream comprising 1,1,2,3-tetrachloropropane and a stream comprisingpentachloropropane isomers and heavier byproducts.
 9. The process ofclaim 8, wherein the stream comprising 1,1,2,3-tetrachloropropane isdehydrochlorinated to produce a stream comprising trichloropropene, andthe trichloropropene stream is chlorinated to produce a streamcomprising 1,1,1,2,3-pentachloropropane and1,1,2,2,3-pentachloropropane.
 10. The process of claim 1, wherein the atleast one chlorination step is carried out in the presence of a freeradical initiator comprising, azobisisobutyronitrile,1,1′-azobis(cyclohexanecarbonitrile), 2,2′-azobis(2,4-dimethylvaleronitrile), and dimethyl 2,2′-azobis(2-methylpropionate), or acombination of these.
 11. The process of claim 1, wherein the at leastone dehydrochlorination is carried out in the presence ofdehydrochlorinating catalyst comprising iron, ferric chloride, aluminumchloride, or a combination of these.
 12. The process of claim 3, whereinthe remainder of the mixture is dehydrochlorinated to provide a streamcomprising 1,1,2,3-tetrachloropropene, 2,3,3,-tetrachloropropane, HCland unreacted pentachloropropanes.
 13. The process of claim 12, whereinthe unreacted pentachloropropanes are dehydrochlorinated to provide amixture comprising 1,1,2,3-tetrachloropropene.
 14. The process of claim3, wherein the 1,2,2,3-tetrachloropropane is recycled to adehydrochlorination step to produce 1,2,3-trichloropropene, and the1,2,3-trichloropropene is chlorinated to produce1,1,2,2,3-pentachloropropane.
 15. A process for preparing2,3,3,3-tetrafluoroprop-1-ene or 1,3,3,3-tetrafluoroprop-1-enecomprising converting a chlorinated propene prepared by the process ofclaim 1 into 2,3,3,3-tetrafluoroprop-1-ene or1,3,3,3-tetrafluoroprop-1-ene.